An 8-endo selective Friedel-Crafts cyclization of vinyloxirane 8 with Co2(CO)6-complexed benzeneacetylene was found to give poly-functional eight-membered cyclic compound 9 in high yields. 相似文献
Electrochemical reactions of manganese(III) complexes, MnIII(L)X (L; salen, salpn, 5-NO2–salen or 5-NO2–salpn, X; Cl, Br or NO2) and MnIII(L’)2X (L’; N-Bu-sal, N-Oct–sal, N-Oct–5-Br–sal or N-Oct–5-NO2–sal, X; Cl or Br), were investigated by voltammetry at a glassy carbon electrode in the absence/presence of Cl− in acetonitrile solution. By the addition of Cl−, oxidation processes of MnIII(L)X and MnIII(L’)2X have been found to be improved from quasi-reversible to reversible, and their oxidation products, [MnIV(L)X]+ and [MnIV(L’)2X]+, were stabilized by the combination with Cl− resulting in [MnIV(L)Cl2] and [MnIV(L’)2Cl2], respectively. On the other hand, the reduction processes of MnIII(L)X and MnIII(L’)2Cl were not so significantly affected by Cl− as those observed for their oxidation. Other types of manganese(III) complexes and iron(III) complex were also investigated. The present study may clarify the role of Cl− being involved in OEC (oxygen-evolving center) in photosystem II. 相似文献
Halorhodopsin (HR) is a transmembrane seven-helix retinal protein, and acts as an inward light-driven Cl− pump. HR from Natronomonas pharaonis (NpHR) can be expressed in Escherichia coli inner membrane in large quantities. Here, we showed that NpHR forms the trimer structure even in the presence of 0.1% (2 m m ) to 1% (20 m m ) dodecyl-β- d -maltoside (DDM), whose concentrations are much higher than the critical micelle concentration (0.17 m m ). This conclusion was drawn from the following observations. (1) NpHR in the DDM solution showed an exciton-coupling circular dichroism (CD) spectrum. (2) From the elution volume of gel filtration, the molecular mass of the NpHR–DDM complex was estimated. After evaluation of the mass of the bound DDM molecules, the mass of NpHR calculated was approximately equal to that of the trimer. (3) The cross-linked NpHR by glutaraldehyde gave the SDS-PAGE corresponding to the trimer. Mass spectra of these samples also support the notion of the trimer. Using the membrane fractions expressing NpHR ( Escherichia coli and Halobacterium salinarum ), CD spectra showed exciton-coupling, which suggests strongly the trimer structure in the cell membrane. 相似文献
Let the dominos fall : Synthesis of the complex DFGH ring system of the title compounds has been accomplished. The approach features simple treatment of the key intermediate with a Brønsted base to afford the tetracyclic cage‐shaped target in one pot through a four‐step domino transformation (see scheme; Mc= monochloromesylate, MOM=methoxymethyl).
Poly(octadecylacrylate) having plural trimethoxysilyl groups in the side chain (co-ODA(n)) was newly synthesized and immobilized onto silica through these groups. The liquid chromatographic behavior of silica-supported co-ODA(n) (Sil-co-ODA(n)) was investigated and compared with that of Sil-ODA(n), in which poly(octadecylacrylate) was immobilized through a terminal trimethoxy group at one side of the polymer main chain. Sil-co-ODA(n) showed higher selectivity for molecular shape, especially molecular planarity of PAHs than Sil-ODA(n). 相似文献
A certified reference material (CRM) is a higher-order calibration material used to enable a traceable analysis. This paper describes the development of a C-peptide CRM (NMIJ CRM 6901-a) by the National Metrology Institute of Japan using two independent methods for amino acid analysis based on isotope-dilution mass spectrometry. C-peptide is a 31-mer peptide that is utilized for the evaluation of β-cell function in the pancreas in clinical testing. This CRM is a lyophilized synthetic peptide having the human C-peptide sequence, and contains deamidated and pyroglutamylated forms of C-peptide. By adding water (1.00 ± 0.01) g into the vial containing the CRM, the C-peptide solution in 10 mM phosphate buffer saline (pH 6.6) is reconstituted. We assigned two certified values that represent the concentrations of total C-peptide (mixture of C-peptide, deamidated C-peptide, and pyroglutamylated C-peptide) and C-peptide. The certified concentration of total C-peptide was determined by two amino acid analyses using pre-column derivatization liquid chromatography-mass spectrometry and hydrophilic chromatography-mass spectrometry following acid hydrolysis. The certified concentration of C-peptide was determined by multiplying the concentration of total C-peptide by the ratio of the relative area of C-peptide to that of the total C-peptide measured by liquid chromatography. The certified value of C-peptide (80.7 ± 5.0) mg/L represents the concentration of the specific entity of C-peptide; on the other hand, the certified value of total C-peptide, (81.7 ± 5.1) mg/L can be used for analyses that does not differentiate deamidated and pyroglutamylated C-peptide from C-peptide itself, such as amino acid analyses and immunochemical assays. 相似文献
The structural and dynamical aspects of alkylammonium salts of a silicodecatungstate [(CH(3))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C1], [(n-C(3)H(7))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C3], [(n-C(4)H(9))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C4], and [(n-C(5)H(11))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C5] were investigated. The results of sorption isotherms, XRD analyses, and solid-state NMR spectroscopy show that facile sorption of solvent molecules, flexibility of structures, and high mobility of alkylammonium cations are crucial to the uniform distribution of reactant and oxidant molecules throughout the bulk solid, which are related to the high catalytic activities for epoxidation of alkenes. 相似文献
Let (M, ω, Φ) be a Hamiltonian T-space and let H í T{H\subseteq T} be a closed Lie subtorus. Under some technical hypotheses on the moment map Φ, we prove that there is no additive torsion
in the integral full orbifold K-theory of the orbifold symplectic quotient [M//H]. Our main technical tool is an extension to the case of moment map level sets the well-known result that components of the
moment map of a Hamiltonian T-space M are Morse-Bott functions on M. As first applications, we conclude that a large class of symplectic toric orbifolds, as well as certain S1-quotients of GKM spaces, have integral full orbifold K-theory that is free of additive torsion. Finally, we introduce the notion of semilocally Delzant which allows us to formulate sufficient conditions under which the hypotheses of the main theorem hold. We illustrate our
results using low-rank coadjoint orbits of type A and B. 相似文献
In this paper we present a unified simple approach to anisotropic Hardy inequalities in various settings. We consider Hardy inequalities which involve a Finsler distance from a point or from the boundary of a domain. The sharpness and the non-attainability of the constants in the inequalities are also proved. 相似文献